Light emitting device having a nitride compound semiconductor and a phosphor containing a garnet fluorescent material

ABSTRACT

The white light emitting diode comprising a light emitting component using a semiconductor as a light emitting layer and a phosphor which absorbs a part of light emitted by the light emitting component and emits light of wavelength different from that of the absorbed light, wherein the light emitting layer of the light emitting component is a nitride compound semiconductor and the phosphor contains garnet fluorescent material activated with cerium which contains at least one element selected from the group consisting of Y, Lu, Sc, La, Gd and Sm, and at least one element selected from the group consisting of Al, Ga and In and, and is subject to less deterioration of emission characteristic even when used with high luminance for a long period of time.

This application is a divisional of coepending Application No.08/902,725, filed Jul. 29, 1997, the entire contents of which are herebyincorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a light emitting diode used in LEDdisplay, back light source, traffic signal, trailway signal,illuminating switch, indicator, etc. More particularly, it relates to alight emitting device (LED) comprising a phosphor, which converts thewavelength of light emitted by a light emitting component and emitslight, and a display device using the light emitting device.

2. Description of Related Art

A light emitting diode is compact and emits light of clear color withhigh efficiency. It is also free from such a trouble as burn-out and hasgood initial drive characteristic, high vibration resistance anddurability to endure repetitive ON/OFF operations, because it is asemiconductor element. Thus it has been used widely in such applicationsas various indicators and various light sources. Recently light emittingdiodes for RGB (red, green and blue) colors having ultra-high luminanceand high efficiency have been developed, and large screen LED displaysusing these light emitting diodes have been put into use. The LEDdisplay can be operated with less power and has such goodcharacteristics as light weight and long life, and is therefore expectedto be more widely used in the future.

Recently, various attempts have been made to make white light sources byusing light emitting diodes. Because the light emitting diode has afavorable emission spectrum to generate monochromatic light, making alight source for white light requires it to arrange three light emittingcomponents of R, G and B closely to each other while diffusing andmixing the light emitted by them. When generating white light with suchan arrangement, there has been such a problem that white light of thedesired tone cannot be generated due to variations in the tone,luminance and other factors of the light emitting component. Also whenthe light emitting components are made of different materials, electricpower required for driving differs from one light emitting diode toanother, making it necessary to apply different voltages different lightemitting components, which leads to complex drive circuit. Moreover,because the light emitting components are semiconductor light emittingcomponents, color tone is subject to variation due to the difference intemperature characteristics, chronological changes and operatingenvironment, or unevenness in color may be caused due to failure inuniformly mixing the light emitted by the light emitting components.Thus light emitting diodes are effective as light emitting devices forgenerating individual colors, although a satisfactory light sourcecapable of emitting white light by using light emitting components hasnot been obtained so far.

In order to solve these problems, the present applicant previouslydeveloped light emitting diodes which convert the color of light, whichis emitted by light emitting components, by means of a fluorescentmaterial disclosed in Japanese Patent Kokai Nos. 5-152609, 7-99345,7-176794 and 8-8614. The light emitting diodes disclosed in thesepublications are such that, by using light emitting components of onekind, are capable of generating light of white and other colors, and areconstituted as follows.

The light emitting diode disclosed in the above gazettes are made bymounting a light emitting component, having a large energy band gap oflight emitting layer, in a cup provided at the tip of a lead frame, andhaving a fluorescent material that absorbs light emitted by the lightemitting component and emits light of a wavelength different from thatof the absorbed light (wavelength conversion), contained in a resin moldwhich covers the light emitting component.

The light emitting diode disclosed as described above capable ofemitting white light by mixing the light of a plurality of sources canbe made by using a light emitting component capable of emitting bluelight and molding the light emitting component with a resin including afluorescent material that absorbs the light emitted by the blue lightemitting diode and emits yellowish light.

However, conventional light emitting diodes have such problems asdeterioration of the fluorescent material leading to color tonedeviation and darkening of the fluorescent material resulting in loweredefficiency of extracting light. Darkening here refers to, in the case ofusing an inorganic fluorescent material such as (Cd, Zn)S fluorescentmaterial, for example, part of metal elements constituting thefluorescent material precipitate or change their properties leading tocoloration, or, in the case of using an organic fluorescent material,coloration due to breakage of double bond in the molecule. Especiallywhen a light emitting component made of a semiconductor having a highenergy band gap is used to improve the conversion efficiency of thefluorescent material (that is, energy of light emitted by thesemiconductor is increased and number of photons having energies above athreshold which can be absorbed by the fluorescent material increases,resulting in more light being absorbed), or the quantity of fluorescentmaterial consumption is decreased (that is, the fluorescent material isirradiated with relatively higher energy), light energy absorbed by thefluorescent material inevitably increases resulting in more significantdegradation of the fluorescent material. Use of the light emittingcomponent with higher intensity of light emission for an extended periodof time causes further more significant degradation of the fluorescentmaterial.

Also the fluorescent material provided in the vicinity of the lightemitting component may be exposed to a high temperature such as risingtemperature of the light emitting component and heat transmitted fromthe external environment (for example, sunlight in case the device isused outdoors).

Further, some fluorescent materials are subject to accelerateddeterioration due to combination of moisture entered from the outside orintroduced during the production process, the light and heat transmittedfrom the light emitting component.

When it comes to an organic dye of ionic property, direct currentelectric field in the vicinity of the chip may cause electrophoresis,resulting in a change in the color tone.

SUMMARY OF THE INVENTION

Thus, an object of the present invention is to solve the problemsdescribed above and provide a light emitting device which experiencesonly extremely low degrees of deterioration in emission light intensity,light emission efficiency and color shift over a long time of use withhigh luminance.

The present applicant completed the present invention through researchesbased on the assumption that a light emitting device having a lightemitting component and a fluorescent material must meet the followingrequirements to achieve the above-mentioned object.

(1) The light emitting component must be capable of emitting light ofhigh luminance with light emitting characteristic which is stable over along time of use.

(2) The fluorescent material being provided in the vicinity of thehigh-luminance light emitting component, must show excellent resistanceagainst light and heat so that the properties thereof do not change evenwhen used over an extended period of time while being exposed to lightof high intensity emitted by the light emitting component (particularlythe fluorescent material provided in the vicinity of the light emittingcomponent is exposed to light of a radiation intensity as high as about30 to 40 times that of sunlight according to our estimate, and isrequired to have more durability against light as light emittingcomponent of higher luminance is used).

(3) With regard to the relationship with the light emitting component,the fluorescent material must be capable of absorbing with highefficiency the light of high monochromaticity emitted by the lightemitting component and emitting light of a wavelength different fromthat of the light emitted by the light emitting component.

Thus the present invention provides a light emitting device, comprisinga light emitting component and a phosphor capable of absorbing a part oflight emitted by the light emitting component and emitting light ofwavelength different from that of the absorbed light; wherein said lightemitting component comprises a nitride compound semiconductorrepresented by the formula: In_(i) Ga_(j) Al_(k) N where 0≦i, 0≦j, 0≦kand i+j+k=1) and said phosphor contains a garnet fluorescent materialcomprising 1) at least one element selected from the group consisting ofY, Lu, Sc, La, Gd and Sm, and 2) at least one element selected from thegroup consisting of Al, Ga and In, and being activated with cerium.

The nitride compound semiconductor (generally represented by chemicalformula In_(i) Ga_(j) Al_(k) N where 0≦i, 0≦j, 0≦k and i+j+k=1)mentioned above contains various materials including InGaN and GaN dopedwith various impurities.

The phosphor mentioned above contains various materials defined asdescribed above, including Y₃ Al₅ O₁₂ :Ce and Gd₃ In₅ O₁₂ :Ce.

Because the light emitting device of the present invention uses thelight emitting component made of a nitride compound semiconductorcapable of emitting light with high luminance, the light emitting deviceis capable of emitting light with high luminance. Also the phosphor usedin the light emitting device has excellent resistance against light sothat the fluorescent properties thereof experience less change even whenused over an extended period of time while being exposed to light ofhigh intensity. This makes it possible to reduce the degradation ofcharacteristics during long period of use and reduce deterioration dueto light of high intensity emitted by the light emitting component aswell as extraneous light (sunlight including ultraviolet light, etc.)during outdoor use, thereby to provide a light emitting device whichexperiences extremely less color shift and less luminance decrease. Thelight emitting device of the present invention can also be used in suchapplications that require response speeds as high as 120 nsec., forexample, because the phosphor used therein allows after glow only for ashort period of time.

The phosphor used in the light emitting diode of the present inventionpreferably contains an yttrium-aluminum-garnet fluorescent material thatcontains Y and Al, which enables it to increase the luminance of thelight emitting device.

In the light emitting device of the present invention, the phosphor maybe a fluorescent material represented by a general formula (Re_(1-r)Sm_(r))₃ (Al_(1-s) Ga_(s))₅ O₁₂ :Ce, where 0≦r<1 and 0≦s≦1 and Re is atleast one selected from Y and Gd, in which case good characteristics canbe obtained similarly to the case where the yttrium-aluminum-garnetfluorescent material is used.

Also in the light emitting device of the present invention, it ispreferable, for the purpose of reducing the temperature dependence oflight emission characteristics (wavelength of emitted light, intensityof light emission, etc.), to use a fluorescent material represented by ageneral formula (Y_(1-p-q-r) Gd_(p) Ce_(q) Sm_(r))₃ (Al_(1-s) Ga_(s))₅O₁₂ as the phosphor, where 0≦p≦0.8, 0.003≦q≦0.2, 0.0003≦r≦0.08 and0≦s≦1.

Also in the light emitting device of the present invention, the phosphormay contain two or more yttrium-aluminum-garnet fluorescent materials,activated with cerium, of different compositions including Y and Al.With this configuration, light of desired color can be emitted bycontrolling the emission spectrum of the phosphor according to theproperty (wavelength of emitted light) of the light emitting component.

Further in the light emitting device of the present invention, in orderto have light of a specified wavelength emitted by the light emittingdevice, it is preferable that the phosphor contains two or morefluorescent materials of different compositions represented by generalformula (Re_(1-r) Sm_(r))₃ (Al_(1-s) Ga_(s))₅ O₁₂ :Ce, where 0≦r<1 and0≦s≦1 and Re is at least one selected from Y and Gd.

Also in the light emitting device of the present invention, in order tocontrol the wavelength of emitted light, the phosphor may contain afirst fluorescent material represented by general formula Y₃ (Al_(1-s)Ga_(s))₅ O₁₂ :Ce and a second fluorescent material represented bygeneral formula Re₃ Al₅ O₁₂ :Ce, where 0≦s≦1 and Re is at least oneselected from Y, Ga and La.

Also in the light emitting device of the present invention, in order tocontrol the wavelength of emitted light, the phosphor may be anyttrium-aluminum-garnet fluorescent material containing a firstfluorescent material and a second fluorescent material, with differentparts of each yttrium being substituted with gadolinium.

Further in the light emitting device of the present invention, it ispreferable that main emission peak of the light emitting component isset within the range from 400 nm to 530 nm and main emission wavelengthof the phosphor is set to be longer than the main emission peak of thelight emitting component. This makes it possible to efficiently emitwhite light.

Further in the light emitting device of the present invention, it ispreferable that the light emitting layer of the light emitting componentcontains gallium nitride semiconductor which contains In, and thephosphor is yttrium-aluminum-garnet fluorescent material wherein part ofAl is substituted by Ga so that the proportion of Ga:Al is within therange from 1:1 to 4:6 and part of Y is substituted by Gd so that theproportion of Y:Gd is within the range from 4:1 to 2:3. Absorptionspectrum of the phosphor which is controlled as described above showsgood agreement with that of light emitted by the light emittingcomponent which contains gallium nitride semiconductor including In asthe light emitting layer, and is capable of improving the conversionefficiency (light emission efficiency). Also the light, generated bymixing blue light emitted by the light emitting component andfluorescent light of the fluorescent material, is a white light of goodcolor rendering and, in this regard, an excellent light emitting devicecan be provided.

The light emitting device according to one embodiment of the presentinvention comprises a substantially rectangular optical guide plateprovided with the light emitting component mounted on one side facethereof via the phosphor and surfaces of which except for one principalsurface are substantially covered with a reflective material, whereinlight emitted by the light emitting component is turned to planar lightby the optical guide plate and the phosphor, and is output from theprincipal surface of the optical guide plate.

The light emitting device according to another embodiment of the presentinvention has a substantially rectangular optical guide plate, which isprovided with the light emitting component mounted on one side facethereof and the phosphor installed on one principal surface withsurfaces thereof except for the principal surface being substantiallycovered with a reflective material, wherein light emitted by the lightemitting component is turned to planar light by the optical guide plateand the phosphor, and is output from the principal surface of theoptical guide plate.

The LED display device according to the present invention has an LEDdisplay device comprising the light emitting devices of the presentinvention arranged in a matrix and a drive circuit which drives the LEDdisplay device according to display data which is input thereto. Thisconfiguration makes it possible to provide a relatively low-priced LEDdisplay device which is capable of high-definition display with lesscolor unevenness due to the viewing angle.

The light emitting diode according to one embodiment of the presentinvention comprises:

a mount lead having a cup and a lead;

an LED chip mounted in the cup of the mount lead with one of electrodesbeing electrically connected to the mount lead;

a transparent coating material filling the cup to cover the LED chip;and

a light emitting diode having a molding material which covers the LEDchip covered with the coating material including the cup of the mountlead, the inner lead and another electrode of the LED chip, wherein

the LED chip is a nitride compound semiconductor and the coatingmaterial contains at least one element selected from the groupconsisting of Y, Lu, Sc, La, Gd and Sm, at least one element selectedfrom the group consisting of Al, Ga and In and a phosphor made of garnetfluorescent material activated with cerium.

The phosphor used in the light emitting diode of the present inventionpreferably contains yttrium-aluminum-garnet fluorescent material thatcontains Y and Al.

In the light emitting diode of the present invention, the phosphor maybe a fluorescent material represented by a general formula (Re_(1-r)Sm_(r))₃ (Al_(1-s) Ga_(s))₅ O₁₂ :Ce, where 0≦r<1 and 0≦s≦1 and Re is atleast one selected from Y and Gd.

Also in the light emitting diode of the present invention, a fluorescentmaterial represented by a general formula (Y_(1-p-q-r) Gd_(p) Ce_(q)Sm_(r))₃ (Al_(1-s) Ga_(s))₅ O₁₂ may be used as the phosphor, where0≦p≦0.8, 0.003≦q≦0.2, 0.0003≦r≦0.08 and 0≦s≦1.

In the light emitting diode of the present invention, the phosphorpreferably contain two or more yttrium-aluminum-garnet fluorescentmaterials, activated with cerium, of different compositions including Yand Al, in order to control the emitted light to a desired wavelength.

In the light emitting diode of the present invention, similarly, two ormore fluorescent materials of different compositions represented by ageneral formula (Re_(1-r) Sm_(r))₃ (Al_(1-s) Ga_(s))₅ O₁₂ :Ce, where0≦r<1 and 0≦s≦1 and Re is at least one selected from Y and Gd may beused as the phosphor in order to control the emitted light to a desiredwavelength.

In the light emitting diode of the present invention, similarly, a firstfluorescent material represented by a general formula Y₃ (Al_(1-s)Ga_(s))₅ O₁₂ :Ce and a second fluorescent material represented by ageneral formula Re₃ Al₅ O₁₂ :Ce, may be used as the phosphor where 0≦s≦1and Re is at least one selected from Y, Ga and La, in order to controlthe emitted light to a desired wavelength.

In the light emitting diode of the present invention, similarly,yttrium-aluminum-garnet fluorescent material a first fluorescentmaterial and a second fluorescent material may be used wherein part ofyttrium being substituted with gadolinium to different degrees ofsubstitution as the phosphor, in order to control the emitted light to adesired wavelength.

Generally, a fluorescent material which absorbs light of a shortwavelength and emits light of a long wavelength has higher efficiencythan a fluorescent material which absorbs light of a long wavelength andemits light of a short wavelength. It is preferable to use a lightemitting component which emits visible light than a light emittingcomponent which emits ultraviolet light that degrades resin (moldingmaterial, coating material, etc.). Thus for the light emitting diode ofthe present invention, for the purpose of improving the light emittingefficiency and ensure long life, it is preferable that main emissionpeak of the light emitting component be set within a relatively shortwavelength range of 400 nm to 530 nm in the visible light region, andmain emission wavelength of the phosphor be set to be longer than themain emission peak of the light emitting component. With thisarrangement, because light converted by the fluorescent material haslonger wavelength than that of light emitted by the light emittingcomponent, it will not be absorbed by the light emitting component evenwhen the light emitting component is irradiated with light which hasbeen reflected and converted by the fluorescent material (since theenergy of the converted light is less than the band gap energy). Thusthe light which has been reflected by the fluorescent material or thelike is reflected by the cup wherein the light emitting component ismounted, making higher efficiency of emission possible.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic sectional view of a lead type light emitting diodeaccording to the embodiment of the present invention.

FIG. 2 is a schematic sectional view of a tip type light emitting diodeaccording to the embodiment of the present invention.

FIG. 3A is a graph showing the excitation spectrum of the garnetfluorescent material activated by cerium used in the first embodiment ofthe present invention.

FIG. 3B is a graph showing the emission spectrum of the garnetfluorescent material activated by cerium used in the first embodiment ofthe present invention.

FIG. 4 is a graph showing the emission spectrum of the light emittingdiode of the first embodiment of the present invention.

FIG. 5A is a graph showing the excitation spectrum of theyttrium-aluminum-garnet fluorescent material activated by cerium used inthe second embodiment of the present invention.

FIG. 5B is a graph showing the emission spectrum of theyttrium-aluminum-garnet fluorescent material activated by cerium used inthe second embodiment of the present invention.

FIG. 6 shows the chromaticity diagram of light emitted by the lightemitting diode of the second embodiment, while points A and B indicatethe colors of light emitted by the light emitting component and points Cand D indicate the colors of light emitted by two kinds of phosphors.

FIG. 7 is a schematic sectional view of the planar light sourceaccording to another embodiment of the present invention.

FIG. 8 is a schematic sectional view of another planar light sourcedifferent from that of FIG. 7.

FIG. 9 is a schematic sectional view of another planar light sourcedifferent from those of FIG. 7 and FIG. 8.

FIG. 10 is a block diagram 10 of a display device which is anapplication of the present invention.

FIG. 11 is a plan view of the LED display device of the display deviceof FIG. 10.

FIG. 12 is a plan view of the LED display device wherein one pixel isconstituted from four light emitting diodes including the light emittingdiode of the present invention and those emitting RGB colors.

FIG. 13A shows the results of durable life test of the light emittingdiodes of Example 1 and Comparative Example 1, showing the results at25° C. and FIG. 13B shows the results of durable life test of the lightemitting diodes of Example 1 and Comparative Example 1, showing theresults at 60° C. and 90% RH.

FIG. 14A shows the results of weatherability test of Example 9 andComparative Example 2 showing the change of luminance retaining ratiowith time and FIG. 14B shows the results of weatherability test ofExample 9 and Comparative Example 2 showing the color tone before andafter the test.

FIG. 15A shows the results of reliability test of Example 9 andComparative Example 2 showing the relationship between the luminanceretaining ratio and time, and FIG. 15B is a graph showing therelationship between color tone and time.

FIG. 16 is a chromaticity diagram showing the range of color tone whichcan be obtained with a light emitting diode which combines thefluorescent materials shown in Table 1 and blue LED having peakwavelength at 465 nm.

FIG. 17 is a chromaticity diagram showing the change in color tone whenthe concentration of fluorescent material is changed in the lightemitting diode which combines the fluorescent materials shown in Table 1and blue LED having peak wavelength at 465 nm.

FIG. 18A shows the emission spectrum of the phosphor (Y₀.6 Gd₀.4)₃ Al₅O₁₂ :Ce of Example 18A.

FIG. 18B shows the emission spectrum of the light emitting component ofExample 18B having the emission peak wavelength of 460 nm.

FIG. 18C shows the emission spectrum of the light emitting diode ofExample 2.

FIG. 19A shows the emission spectrum of the phosphor (Y₀.2 Gd₀.8)₃ Al₅O₁₂ :Ce of Example 5.

FIG. 19B shows the emission spectrum of the light emitting component ofExample 5 having the emission peak wavelength of 450 nm.

FIG. 19C shows the emission spectrum of the light emitting diode ofExample 5.

FIG. 20A shows the emission spectrum of the phosphor Y₃ Al₅ O₁₂ :Ce ofExample 6.

FIG. 20B shows the emission spectrum of the light emitting component ofExample 6 having the emission peak wavelength of 450 nm.

FIG. 20C shows the emission spectrum of the light emitting diode ofExample 6.

FIG. 21A shows the emission spectrum of the phosphor Y₃ (Al₀.5 Ga₀.5)₅O₁₂ :Ce of the seventh embodiment of the present invention

FIG. 21B shows the emission spectrum of the light emitting component ofExample 7 having the emission peak wavelength of 450 nm.

FIG. 21C shows the emission spectrum of the light emitting diode ofExample 7.

FIG. 22A shows the emission spectrum of the phosphor (Y₀.8 Gd₀.2)₃ Al₅O₁₂ :Ce of Example 11.

FIG. 22B shows the emission spectrum of the phosphor (Y₀.4 Gd₀.6)₃ Al₅O₁₂ :Ce of Example 11.

FIG. 22C shows the emission spectrum of the light emitting component ofExample 11 having the emission peak wavelength of 470 nm.

FIG. 23 shows the emission spectrum of the light emitting diode ofExample 11.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Now referring to the attached drawings, preferred embodiments of thepresent invention will be described below.

A light emitting diode 100 of FIG. 1 is a lead type light emitting diodehaving a mount lead 105 and an inner lead 106, wherein a light emittingcomponent 102 is installed on a cup 105a of the mount lead 105, and thecup 105a is filled with a coating resin 101 which contains a specifiedphosphor to cover the light emitting component 102 and is molded inresin. An n electrode and a p electrode of the light emitting component102 are connected to the mount lead 105 and the inner lead 106,respectively, by means of wires 103.

In the light emitting diode constituted as described above, part oflight emitted by the light emitting component (LED chip) 102(hereinafter referred to as LED light) excites the phosphor contained inthe coating resin 101 to generate fluorescent light having a wavelengthdifferent from that of LED light, so that the fluorescent light emittedby the phosphor and LED light which is output without contributing tothe excitation of the phosphor are mixed and output. As a result, thelight emitting diode 100 also outputs light having a wavelengthdifferent from that of LED light emitted by the light emitting component102.

FIG. 2 shows a chip type light emitting diode, wherein light emittingdiode (LED chip) 202 is installed in a recess of a casing 204 which isfilled with a coating material which contains a specified phosphor toform a coating 201. The light emitting component 202 is fixed by usingan epoxy resin or the like which contains Ag, for example, and an nelectrode and a p electrode of the light emitting component 202 areconnected to metal terminals 205 installed on the casing 204 by means ofconductive wires 203. In the chip type light emitting diode constitutedas described above, similarly to the lead type light emitting diode ofFIG. 1, fluorescent light emitted by the phosphor and LED light which istransmitted without being absorbed by the phosphor are mixed and output,so that the light emitting diode 200 also outputs light having awavelength different from that of LED light emitted by the lightemitting component 202.

The light emitting diode containing the phosphor as described above hasthe following features.

1. Light emitted by a light emitting component (LED) is usually emittedthrough an electrode which supplies electric power to the light emittingcomponent. Emitted light is partly blocked by the electrode formed onthe light emitting component resulting in a particular emission pattern,and is therefore not emitted uniformly in every direction. The lightemitting diode which contains the fluorescent material, however, canemit light uniformly over a wide range without forming undesirableemission pattern because the light is emitted after being diffused bythe fluorescent material.

2. Although light emitted by the light emitting component (LED) has amonochromatic peak, the peak is broad and has high color renderingproperty. This characteristic makes an indispensable advantage for anapplication which requires wavelengths of a relatively wide range. Lightsource for an optical image scanner, for example, is desirable to have awider emission peak.

The light emitting diodes of the first and second embodiments to bedescribed below have the configuration shown in FIG. 1 or FIG. 2 whereina light emitting component which uses nitride compound semiconductorhaving relatively high energy in the visible region and a particularphosphor are combined, and have such favorable properties as capabilityto emit light of high luminance and less degradation of light emissionefficiency and less color shift over an extended period of use.

In general, a fluorescent material which absorbs light of a shortwavelength and emits light of a long wavelength has higher efficiencythan a fluorescent material which absorbs light of a long wavelength andemits light of a short wavelength, and therefore it is preferable to usea nitride compound semiconductor light emitting component which iscapable of emitting blue light of short wavelength. It needs not to saythat the use of a light emitting component having high luminance ispreferable.

A phosphor to be used in combination with the nitride compoundsemiconductor light emitting component must have the followingrequirements:

1. Excellent resistance against light to endure light of a highintensity for a long period of time, because the fluorescent material isinstalled in the vicinity of the light emitting components 102, 202 andis exposed to light of intensity as high as about 30 to 40 times that ofsun light.

2. Capability to efficiently emit light in blue region for theexcitation by means of the light emitting components 102, 202. Whenmixing of colors is used, should be capable of emitting blue light, notultraviolet ray, with a high efficiency.

3. capability to emit light from green to red regions for the purpose ofmixing with blue light to generate white light.

4. Good temperature characteristic suitable for location in the vicinityof the light emitting components 102, 202 and the resultant influence oftemperature difference due to heat generated by the chip when lighting.

5. Capability to continuously change the color tone in terms of theproportion of composition or ratio of mixing a plurality of fluorescentmaterials.

6. Weatherability for the operating environment of the light emittingdiode.

Embodiment 1

The light emitting diode of the first embodiment of the presentinvention employs a gallium nitride compound semiconductor element whichhas high-energy band gap in the light emitting layer and is capable ofemitting blue light, and a garnet phosphor activated with cerium incombination. With this configuration, the light emitting diode of thefirst embodiment can emit white light by blending blue light emitted bythe light emitting components 102, 202 and yellow light emitted by thephosphor excited by the blue light.

Because the garnet phosphor activated with cerium which is used in thelight emitting diode of the first embodiment has light resistance andweatherability, it can emit light with extremely small degrees of colorshift and decrease in the luminance of emitted light even whenirradiated by very intense light emitted by the light emittingcomponents 102, 202 located in the vicinity over a long period of time.

Components of the light emitting diode of the first embodiment will bedescribed in detail below.

(Phosphor)

The phosphor used in the light emitting diode of the first embodiment isa phosphor which, when excited by visible light or ultraviolet rayemitted by the semiconductor light emitting layer, emits light of awavelength different from that of the exciting light. The phosphor isspecifically garnet fluorescent material activated with cerium whichcontains at least one element selected from Y, Lu, Sc, La, Gd and Sm andat least one element selected from Al, Ga and In. According to thepresent invention, the fluorescent material is preferablyyttrium-aluminum-garnet fluorescent material (YAG phosphor) activatedwith cerium, or a fluorescent material represented by general formula(Re_(1-r) Sm_(r))₃ (Al_(1-s) Ga_(s))₅ O₁₂ :Ce, where 0≦r<1 and 0≦s≦1,and Re is at least one selected from Y and Gd. In case the LED lightemitted by the light emitting component employing the gallium nitridecompound semiconductor and the fluorescent light emitted by the phosphorhaving yellow body color are in the relation of complementary colors,white color can be output by blending the LED light and the fluorescentlight.

In the first embodiment, because the phosphor is used by blending with aresin which makes the coating resin 101 and the coating material 201(detailed later), color tone of the light emitting diode can be adjustedincluding white and incandescent lamp color by controlling the mixingproportion with the resin or the quantity used in filling the cup 105 orthe recess of the casing 204 in accordance to the wavelength of lightemitted by the gallium nitride light emitting component.

Distribution of the phosphor concentration has influence also on thecolor blending and durability. That is, when the concentration ofphosphor increases from the surface of the coating or molding where thephosphor is contained toward the light emitting component, it becomesless likely to be affected by extraneous moisture thereby making iteasier to suppress the deterioration due to moisture. On the other hand,when the concentration of phosphor increases from the light emittingcomponent toward the surface of the molding, it becomes more likely tobe affected by extraneous moisture, but less likely to be affected bythe heat and radiation from the light emitting component, thus making itpossible to suppress the deterioration of the phosphor. Suchdistributions of the phosphor concentration can be achieved by selectingor controlling the material which contains the phosphor, formingtemperature and viscosity, and the configuration and particledistribution of the phosphor.

By using the phosphor of the first embodiment, light emitting diodehaving excellent emission characteristics can be made, because thefluorescent material has enough light resistance for high-efficientoperation even when arranged adjacent to or in the vicinity of the lightemitting components 102, 202 with radiation intensity (Ee) within therange from 3 Wcm⁻² to 10 Wcm⁻².

The phosphor used in the first embodiment is, because of garnetstructure, resistant to heat, light and moisture, and is thereforecapable of absorbing excitation light having a peak at a wavelength near450 nm as shown in FIG. 3A. It also emits light of broad spectrum havinga peak near 580 nm tailing out to 700 nm as shown in FIG. 3B. Moreover,efficiency of excited light emission in a region of wavelengths 460 nmand higher can be increased by including Gd in the crystal of thephosphor of the first embodiment. When the Gd content is increased,emission peak wavelength is shifted toward longer wavelength and theentire emission spectrum is shifted toward longer wavelengths. Thismeans that, when emission of more reddish light is required, it can beachieved by increasing the degree of substitution with Gd. When the Gdcontent is increased, luminance of light emitted by photoluminescenceunder blue light tends to decrease.

Especially when part of Al is substituted with Ga among the compositionof YAG fluorescent material having garnet structure, wavelength ofemitted light shifts toward shorter wavelength and, when part of Y issubstituted with Gd, wavelength of emitted light shifts toward longerwavelength.

Table 1 shows the composition and light emitting characteristics of YAGfluorescent material represented by general formula (Y_(1-a) Gd_(a))₃(Al_(1-b) Ga_(b))₅ O₁₂ :Ce.

                  TABLE 1                                                         ______________________________________                                                             CIE                                                        Gd content Ga content chromaticity                                            a (molar b (molar coordinates Luminance Effi-                               No.  ratio)    ratio)    x    y    Y       ciency                             ______________________________________                                        1    0.0       0.0       0.41 0.56 100     100                                  2 0.0 0.4 0.32 0.56 61 63                                                     3 0.0 0.5 0.29 0.54 55 67                                                     4 0.2 0.0 0.45 0.53 102 108                                                   5 0.4 0.0 0.47 0.52 102 113                                                   6 0.6 0.0 0.49 0.51 97 113                                                    7 0.8 0.0 0.50 0.50 72 86                                                   ______________________________________                                    

Values shown in Table 1 were measured by exciting the fluorescentmaterial with blue light of 460 nm. Luminance and efficiency in Table 1are given in values relative to those of material No.1 which are set to100.

When substituting Al with Ga, the proportion is preferably within therange from Ga:Al=1:1 to 4:6 in consideration of the emission efficiencyand emission wavelength. Similarly, when substituting Y with Gd, theproportion is preferably within the range from Y:Gd=9:1 to 1:9, and morepreferably from 4:1 to 2:3. It is because a degree of substitution withGd below 20% results in a color of greater green component and less redcomponent, and a degree of substitution with Gd above 60% results inincreased red component but rapid decrease in luminance. When the ratioY:Gd of Y and Gd in the YAG fluorescent material is set within the rangefrom 4:1 to 2:3, in particular, a light emitting diode capable ofemitting white light substantially along the black body radiation locuscan be made by using one kind of yttrium-aluminum-garnet fluorescentmaterial, depending on the emission wavelength of the light emittingcomponent. When the ratio Y:Gd of Y and Gd in the YAG fluorescentmaterial is set within the range from 2:3 to 1:4, a light emitting diodecapable of emitting light of incandescent lamp can be made though theluminance is low. When the content (degree of substitution) of Ce is setwithin the range from 0.003 to 0.2, the relative luminous intensity oflight emitting diode of not less than 70% can be achieved. When thecontent is less than 0.003, luminous intensity decreases because thenumber of excited emission centers of photoluminescence due to Cedecreases and, when the content is greater than 0.2, density quenchingoccurs.

Thus the wavelength of the emitted light can be shifted to a shorterwavelength by substituting part of Al of the composition with Ga, andthe wavelength of the emitted light can be shifted to a longerwavelength by substituting part of Y of the composition with Gd. In thisway, the light color of emission can be changed continuously by changingthe composition. Also the fluorescent material is hardly excited by Hgemission lines which have such wavelengths as 254 nm and 365 nm, but isexcited with higher efficiency by LED light emitted by a blue lightemitting component having a wavelength around 450 nm. Thus thefluorescent material has ideal characteristics for converting blue lightof nitride semiconductor light emitting component into white light, suchas the capability of continuously changing the peak wavelength bychanging the proportion of Gd.

According to the first embodiment, the efficiency of light emission ofthe light emitting diode can be further improved by combining the lightemitting component employing gallium nitride semiconductor and thephosphor made by adding rare earth element samarium (Sm) toyttrium-aluminum-garnet fluorescent materials (YAG) activated withcerium.

Material for making such a phosphor is made by using oxides of Y, Gd,Ce, Sm, Al and Ga or compounds which can be easily converted into theseoxides at high temperature, and sufficiently mixing these materials instoichiometrical proportions. This mixture is mixed with an appropriatequantity of a fluoride such as ammonium fluoride used as a flux, andfired in a crucible at a temperature from 1350 to 1450° C. in air for 2to 5 hours. Then the fired material is ground by a ball mill in water,washed, separated, dried and sieved thereby to obtain the desiredmaterial.

In the producing process described above, the mixture material may alsobe made by dissolving rare earth elements Y, Gd, Ce and Sm instoichiometrical proportions in an acid, coprecipitating the solutionwith oxalic acid and firing the coprecipitate to obtain an oxide of thecoprecipitate, and then mixing it with aluminum oxide and gallium oxide.

The phosphor represented by the general formula (Y_(1-p-q-r) Gd_(p)Ce_(q) Sm_(r))₃ Al₅ O₁₂ can emit light of wavelengths 460 nm and longerwith higher efficiency upon excitation, because Gd is contained in thecrystal. When the content of gadolinium is increased, peak wavelength ofemission shifts from 530 nm to a longer wavelength up to 570 nm, whilethe entire emission spectrum also shifts to longer wavelengths. Whenlight of stronger red shade is needed, it can be achieved by increasingthe amount of Gd added for substitution. When the content of Gd isincreased, luminance of photoluminescence with blue light graduallydecreases. Therefore, value of p is preferably 0.8 or lower, or morepreferably 0.7 or lower. Further more preferably it is 0.6 or lower.

The phosphor represented by the general formula (Y_(1-p-q-r) Gd_(p)Ce_(q) Sm_(r))₃ Al₅ O₁₂ including Sm can be made subject to lessdependence on temperature regardless of the increased content of Gd.That is, the phosphor, when Sm is contained, has greatly improvedemission luminance at higher temperatures. Extent of the improvementincreases as the Gd content is increased. Temperature characteristic canbe greatly improved particularly by the addition of Sm in the case offluorescent material of such a composition as red shade is strengthenedby increasing the content of Gd, because it has poor temperaturecharacteristics. The temperature characteristic mentioned here ismeasured in terms of the ratio (%) of emission luminance of thefluorescent material at a high temperature (200° C.) relative to theemission luminance of exciting blue light having a wavelength of 450 nmat the normal temperature (25° C.).

The proportion of Sm is preferably within the range of 0.0003≦r≦0.08 togive temperature characteristic of 60% or higher. The value of r belowthis range leads to less effect of improving the temperaturecharacteristic. When the value of r is above this range, on thecontrary, the temperature characteristic deteriorates. The range of0.0007≦r≦0.02 for the proportion of Sm where temperature characteristicbecomes 80% or higher is more desirable.

The proportion q of Ce is preferably in a range of 0.003≦q≦0.2, whichmakes relative emission luminance of 70% or higher possible. Therelative emission luminance refers to the emission luminance in terms ofpercentage to the emission luminance of a fluorescent material whereq=0.03.

When the proportion q of Ce is 0.003 or lower, luminance decreasesbecause the number of excited emission centers of photoluminescence dueto Ce decreases and, when the q is greater than 0.2, density quenchingoccurs. Density quenching refers to the decrease in emission intensitywhich occurs when the concentration of an activation agent added toincrease the luminance of the fluorescent material is increased beyondan optimum level.

For the light emitting diode of the present invention, a mixture of twoor more kinds of phosphors having compositions of (Y_(1-p-q-r) Gd_(p)Ce_(q) Sm_(r))₃ Al₅ O₁₂ having different contents of Al, Ga, Y and Gs orSm may also be used. This increases the RGB components and enables theapplication, for example, for a full-color liquid crystal display deviceby using a color filter.

(Light emitting components 102, 202)

The light emitting component is preferably embedded in a moldingmaterial as shown in FIG. 1 and FIG. 2. The light emitting componentused in the light emitting diode of the present invention is a galliumnitride compound semiconductor capable of efficiently exciting thegarnet fluorescent materials activated with cerium. The light emittingcomponents 102, 202 employing gallium nitride compound semiconductor aremade by forming a light emitting layer of gallium nitride semiconductorsuch as InGaN on a substrate in the MOCVD process. The structure of thelight emitting component may be homostructure, heterostructure ordouble-heterostructure which have MIS junction, PIN junction or PNjunction. Various wavelengths of emission can be selected depending onthe material of the semiconductor layer and the crystallinity thereof.It may also be made in a single quantum well structure or multiplequantum well structure where a semiconductor activation layer is formedas thin as quantum effect can occur. According to the present invention,a light emitting diode capable of emitting with higher luminance withoutdeterioration of the phosphor can be made by making the activation layerof the light emitting component in single quantum well structure ofInGaN.

When a gallium nitride compound semiconductor is used, while sapphire,spinnel, SiC, Si, ZnO or the like may be used as the semiconductorsubstrate, use of sapphire substrate is preferable in order to formgallium nitride of good crystallinity. A gallium nitride semiconductorlayer is formed on the sapphire substrate to form a PN junction via abuffer layer of GaN, AlN, etc. The gallium nitride semiconductor has Ntype conductivity under the condition of not doped with any impurity,although in order to form an N type gallium nitride semiconductor havingdesired properties (carrier concentration, etc.) such as improved lightemission efficiency, it is preferably doped with N type dopant such asSi, Ge, Se, Te, and C. In order to form a P type gallium nitridesemiconductor, on the other hand, it is preferably doped with P typedopant such as Zn, Mg, Be, Ca, Sr and Ba. Because it is difficult toturn a gallium nitride compound semiconductor to P type simply by dopinga P type dopant, it is preferable to treat the gallium nitride compoundsemiconductor doped with P type dopant in such process as heating in afurnace, irradiation with low-speed electron beam and plasmairradiation, thereby to turn it to P type. After exposing the surfacesof P type and N type gallium nitride semiconductors by the etching orother process, electrodes of the desired shapes are formed on thesemiconductor layers by sputtering or vapor deposition.

Then the semiconductor wafer which has been formed is cut into pieces bymeans of a dicing saw, or separated by an external force after cuttinggrooves (half-cut) which have width greater than the blade edge width.Or otherwise, the wafer is cut into chips by scribing grid pattern ofextremely fine lines on the semiconductor wafer by means of a scriberhaving a diamond stylus which makes straight reciprocal movement. Thusthe light emitting component of gallium nitride compound semiconductorcan be made.

In order to emit white light with the light emitting diode of the firstembodiment, wavelength of light emitted by the light emitting componentis preferably from 400 nm to 530 nm inclusive in consideration of thecomplementary color relationship with the phosphor and deterioration ofresin, and more preferably from 420 nm to 490 nm inclusive. It isfurther more preferable that the wavelength be from 450 nm to 475 nm, inorder to improve the emission efficiency of the light emitting componentand the phosphor. Emission spectrum of the white light emitting diode ofthe first embodiment is shown in FIG. 4. The light emitting componentshown here is of lead type shown in FIG. 1, which employs the lightemitting component and the phosphor of the first embodiment to bedescribed later. In FIG. 4, emission having a peak around 450 nm is thelight emitted by the light emitting component, and emission having apeak around 570 nm is the photoluminescent emission excited by the lightemitting component.

FIG. 16 shows the colors which can be represented by the white lightemitting diode made by combining the fluorescent material shown in Table1 and blue LED (light emitting component) having peak wavelength 465 nm.Color of light emitted by this white light emitting diode corresponds toa point on a straight line connecting a point of chromaticity generatedby the blue LED and a point of chromaticity generated by the fluorescentmaterial, and therefore the wide white color region (shaded portion inFIG. 16) in the central portion of the chromaticity diagram can be fullycovered by using the fluorescent materials 1 to 7 in Table 1. FIG. 17shows the change in emission color when the contents of fluorescentmaterials in the white light emitting diode is changed. Contents offluorescent materials are given in weight percentage to the resin usedin the coating material. As will be seen from FIG. 17, color of thelight approaches that of the fluorescent materials when the content offluorescent material is increased and approaches that of blue LED whenthe content of fluorescent material is decresed.

According to the present invention, a light emitting component whichdoes not excite the fluorescent material may be used together with thelight emitting component which emits light that excites the fluorescentmaterial. Specifically, in addition to the fluorescent material which isa nitride compound semiconductor capable of exciting the fluorescentmaterial, a light emitting component having a light emitting layer madeof gallium phosphate, gallium aluminum arsenide, gallium arsenicphosphate or indium aluminum phosphate is arranged together. With thisconfiguration, light emitted by the light emitting component which doesnot excite the fluorescent material is radiated to the outside withoutbeing absorbed by the fluorescent material, making a light emittingdiode which can emit red/white light.

Other components of the light emitting diodes of FIG. 1 and FIG. 2 willbe described below.

(Conductive wires 103, 203)

The conductive wires 103, 203 should have good electric conductivity,good thermal conductivity and good mechanical connection with theelectrodes of the light emitting components 102, 202. Thermalconductivity is preferably 0.01 cal/(s)(cm²)(° C./cm) or higher, andmore preferably 0.5 cal/(s)(cm²)(° C./cm) or higher. For workability,diameter of the conductive wire is preferably from 10 μm to 45 μminclusive. Even when the same material is used for both the coatingincluding the fluorescent material and the molding, because of thedifference in thermal expansion coefficient due to the fluorescentmaterial contained in either of the above two materials, the conductivewire is likely to break at the interface. For this reason, diameter ofthe conductive wire is preferably not less than 25 μm and, for thereason of light emitting area and ease of handling, preferably within 35μm. The conductive wire may be a metal such as gold, copper, platinumand aluminum or an alloy thereof. When a conductive wire of suchmaterial and configuration is used, it can be easily connected to theelectrodes of the light emitting components, the inner lead and themount lead by means of a wire bonding device.

(Mount lead 105)

The mount lead 105 comprises a cup 105a and a lead 105b, and it sufficesto have a size enough for mounting the light emitting component 102 withthe wire bonding device in the cup 105a. In case a plurality of lightemitting components are installed in the cup and the mount lead is usedas common electrode for the light emitting component, because differentelectrode materials may be used, sufficient electrical conductivity andgood conductivity with the bonding wire and others are required. Whenthe light emitting component is installed in the cup of the mount leadand the cup is filled with the fluorescent material, light emitted bythe fluorescent material is, even if isotropic, reflected by the cup ina desired direction and therefore erroneous illumination due to lightfrom other light emitting diode mounted nearby can be prevented.Erroneous illumination here refers to such a phenomenon as other lightemitting diode mounted nearby appearing as though lighting despite notbeing supplied with power.

Bonding of the light emitting component 102 and the mount lead 105 withthe cup 105a can be achieved by means of a thermoplastic resin such asepoxy resin, acrylic resin and imide resin. When a face-down lightemitting component (such a type of light emitting component as emittedlight is extracted from the substrate side and is configured formounting the electrodes to oppose the cup 105a) is used, Ag paste,carbon paste, metallic bump or the like can be used for bonding andelectrically connecting the light emitting component and the mount leadat the same time. Further, in order to improve the efficiency of lightutilization of the light emitting diode, surface of the cup of the mountlead whereon the light emitting component is mounted may bemirror-polished to give reflecting function to the surface. In thiscase, the surface roughness is preferably from 0.1 S to 0.8 S inclusive.Electric resistance of the mount lead is preferably within 300 μΩ-cm andmore preferably within 3 μΩ-cm. When mounting a plurality of lightemitting components on the mount lead, the light emitting componentsgenerate significant amount of heat and therefore high thermalconductivity is required. Specifically, the thermal conductivity ispreferably 0.01 cal/(s)(cm²)(° C./cm) or higher, and more preferably 0.5cal/(s)(cm²)(° C./cm) or higher. Materials which satisfy theserequirements contain steel, copper, copper-clad steel, copper-clad tinand metallized ceramics.

(Inner lead 106)

The inner lead 106 is connected to one of electrodes of the lightemitting component 102 mounted on the mount lead 105 by means ofconductive wire or the like. In the case of a light emitting diode wherea plurality of the light emitting components are installed on the mountlead, it is necessary to arrange a plurality of inner leads 106 in sucha manner that the conductive wires do not touch each other. For example,contact of the conductive wires with each other can be prevented byincreasing the area of the end face where the inner lead is wire-bondedas the distance from the mount lead increases so that the space betweenthe conductive wires is secured. Surface roughness of the inner lead endface connecting with the conductive wire is preferably from 1.6 S to 10S inclusive in consideration of close contact.

In order to form the inner lead in a desired shape, it may be punched bymeans of a die. Further, it may be made by punching to form the innerlead then pressurizing it on the end face thereby to control the areaand height of the end face.

The inner lead is required to have good connectivity with the bondingwires which are conductive wires and have good electrical conductivity.Specifically, the electric resistance is preferably within 300 μΩ·cm andmore preferably within 3 μΩ·cm. Materials which satisfy theserequirements contain iron, copper, iron-containing copper,tin-containing copper, copper-, gold- or silver-plated aluminum, ironand copper.

(Coating material 101)

The coating material 101 is provided in the cup of the mount lead apartfrom the molding material 104 and, in the first embodiment, contains thephosphor which converts the light emitted by the light emittingcomponent. The coating material may be a transparent material havinggood weatherability such as epoxy resin, urea resin and silicon orglass. A dispersant may be used together with the phosphor. As thedispersant, barium titanate, titanium oxide, aluminum oxide, silicondioxide and the like are preferably used. When the fluorescent materialis formed by sputtering, coating material may be omitted. In this case,a light emitting diode capable of bending colors can be made bycontrolling the film thickness or providing an aperture in thefluorescent material layer.

(Molding material 104)

The molding 104 has the function to protect the light emitting component102, the conductive wire 103 and the coating material 101 which containsphosphor from external disturbance. According to the first embodiment,it is preferable that the molding material 104 further contain adispersant, which can unsharpen the directivity of light from the lightemitting component 102, resulting in increased angle of view. Themolding material 104 has-the function of lens to focus or diffuse thelight emitted by the light emitting component. Therefore, the moldingmaterial 104 may be made in a configuration of convex lens or concavelens, and may have an elliptic shape when viewed in the direction ofoptical axis, or a combination of these. Also the molding material 104may be made in a structure of multiple layers of different materialsbeing laminated. As the molding material 104, transparent materialshaving high weatherability such as epoxy resin, urea resin, siliconresin or glass is preferably employed. As the dispersant, bariumtitanate, titanium oxide, aluminum oxide, silicon dioxide and the likecan be used. In addition to the dispersant, phosphor may also becontained in the molding material. Namely, according to the presentinvention, the phosphor may be contained either in the molding materialor in the coating material. When the phosphor is contained in themolding material, angle of view can be further increased. The phosphormay also be contained in both the coating material and the moldingmaterial. Further, a resin including the phosphor may be used as thecoating material while using glass, different from the coating material,as the molding material. This makes it possible to manufacture a lightemitting diode which is less subject to the influence of moisture withgood productivity. The molding and the coating may also be made of thesame material in order to match the refractive index, depending on theapplication. According to the present invention, adding the dispersantand/or a coloration agent in the molding material has the effects ofmasking the color of the fluorescent material obscured and improving thecolor mixing performance. That is, the fluorescent material absorbs bluecomponent of extraneous light and emits light thereby to give such anappearance as though colored in yellow. However, the dispersantcontained in the molding material gives milky white color to the moldingmaterial and the coloration agent renders a desired color. Thus thecolor of the fluorescent material will not be recognized by theobserver. In case the light emitting component emits light having mainwavelength of 430 nm or over, it is more preferable that ultravioletabsorber which serves as light stabilizer be contained.

Embodiment 2

The light emitting diode of the second embodiment of the presentinvention is made by using an element provided with gallium nitridecompound semiconductor which has high-energy band gap in the lightemitting layer as the light emitting component and a fluorescentmaterial including two or more kinds of phosphors of differentcompositions, or preferably yttrium-aluminum-garnet fluorescentmaterials activated with cerium as the phosphor. With thisconfiguration, a light emitting diode which allows to give a desiredcolor tone by controlling the contents of the two or more fluorescentmaterials can be made even when the wavelength of the LED light emittedby the light emitting component deviates from the desired value due tovariations in the production process. In this case, emission color ofthe light emitting diode can be made constantly using a fluorescentmaterial having a relatively short emission wavelength for a lightemitting component of a relatively short emission wavelength and using afluorescent material having a relatively long emission wavelength for alight emitting component of a relatively long emission wavelength.

As for the fluorescent material, a fluorescent material represented bygeneral formula (Re_(1-r) Sm_(r))₃ (Al_(1-s) Ga_(s))₅ O₁₂ :Ce may alsobe used as the phosphor. Here 0≦r<1 and 0≦s≦1, and Re is at least oneselected from Y, Gd and La. This configuration makes it possible tominimize the denaturing of the fluorescent material even when thefluorescent material is exposed to high-intensity high-energy visiblelight emitted by the light emitting component for a long period of timeor when used under various environmental conditions, and therefore alight emitting diode which is subject to extremely insignificant colorshift and emission luminance decrease and has the desired emissioncomponent of high luminance can be made.

(Phosphor of the second embodiment)

Now the phosphor used in the light emitting component of the secondembodiment will be described in detail below. The second embodiment issimilar to the first embodiment, except that two or more kinds ofphosphors of different compositions activated with cerium are used asthe phosphor, as described above, and the method of using thefluorescent material is basically the same.

Similarly to the case of the first embodiment, the light emitting diodecan be given high weatherability by controlling the distribution of thephosphor (such as tapering the concentration with the distance from thelight emitting component). Such a distribution of the phosphorconcentration can be achieved by selecting or controlling the materialwhich contains the phosphor, forming temperature and viscosity, and theconfiguration and particle distribution of the phosphor. Thus accordingto the second embodiment, distribution of the fluorescent materialconcentration is determined according to the operating conditions. Alsoaccording to the second embodiment, efficiency of light emission can beincreased by designing the arrangement of the two or more kinds offluorescent materials (for example, arranging in the order of nearnessto the light emitting component) according to the light generated by thelight emitting component.

With the configuration of the second embodiment, similarly to the firstembodiment, light emitting diode has high efficiency and enough lightresistance even when arranged adjacent to or in the vicinity ofrelatively high-output light emitting component with radiation intensity(Ee) within the range from 3 Wcm⁻² to 10 Wcm⁻² can be made.

The yttrium-aluminum-garnet fluorescent material activated with cerium(YAG fluorescent material) used in the second embodiment has garnetstructure similarly to the case of the first embodiment, and istherefore resistant to heat, light and moisture. The peak wavelength ofexcitation of the yttrium-aluminum-garnet fluorescent material of thesecond embodiment can be set near 450 nm as indicated by the solid linein FIG. 5A, and the peak wavelength of emission can be set near 510 nmas indicated by the solid line in FIG. 5B, while making the emissionspectrum so broad as to tail out to 700 nm. This makes it possible toemit green light. The peak wavelength of excitation of anotheryttrium-aluminum-garnet fluorescent material activated with cerium ofthe second embodiment can be set near 450 nm as indicated by the dashedline in FIG. 5A, and the peak wavelength of emission can be set near 600nm as indicated by the dashed line in FIG. 5B, while making the emissionspectrum so broad as to tail out to 750 nm. This makes it possible toemit red light.

Wavelength of the emitted light is shifted to a shorter wavelength bysubstituting part of Al, among the constituents of the YAG fluorescentmaterial having garnet structure, with Ga, and the wavelength of theemitted light is shifted to a longer wavelength by substituting part ofY with Gd and/or La. Proportion of substituting Al with Ga is preferablyfrom Ga:Al=1:1 to 4:6 in consideration of the light emitting efficiencyand the wavelength of emission. Similarly, proportion of substituting Ywith Gd and/or La is preferably from Y:Gd and/or La=9:1 to 1:9, or morepreferably from Y:Gd and/or La=4:1 to 2:3. Substitution of less than 20%results in an increase of green component and a decrease of redcomponent. Substitution of 80% or greater part, on the other hand,increases red component but decreases the luminance steeply.

Material for making such a phosphor is made by using oxides of Y, Gd,Ce, La, Al, Sm and Ga or compounds which can be easily converted intothese oxides at high temperature, and sufficiently mixing thesematerials in stoichiometrical proportions. Or either, mixture materialis obtained by dissolving rare earth elements Y, Gd, Ce, La and Sm instoichiometrical proportions in acid, coprecipitating the solutionoxalic acid and firing the coprecipitate to obtain an oxide of thecoprecipitate, which is then mixed with aluminum oxide and galliumoxide. This mixture is mixed with an appropriate quantity of a fluoridesuch as ammonium fluoride used as a flux, and fired in a crucible at atemperature from 1350 to 1450° C. in air for 2 to 5 hours. Then thefired material is ground by a ball mill in water, washed, separated,dried and sieved thereby to obtain the desired material.

In the second embodiment, the two or more kinds ofyttrium-aluminum-garnet fluorescent materials activated with cerium ofdifferent compositions may be either used by mixing or arrangedindependently (laminated, for example). When the two or more kinds offluorescent materials are mixed, color converting portion can be formedrelatively easily and in a manner suitable for mass production. When thetwo or more kinds of fluorescent materials are arranged independently,color can be adjusted after forming it by laminating the layers until adesired color can be obtained. Also when arranging the two or more kindsof fluorescent materials independently, it is preferable to arrange afluorescent material that absorbs light from the light emittingcomponent of a shorter wavelength near to the LED element, and afluorescent material that absorbs light of a longer wavelength away fromthe LED element. This arrangement enables efficient absorption andemission of light.

The light emitting diode of the second embodiment is made by using twoor more kinds of yttrium-aluminum-garnet fluorescent materials ofdifferent compositions as the fluorescent materials, as described above.This makes it possible to make a light emitting diode capable ofemitting light of desired color efficiently. That is, when wavelength oflight emitted by the semiconductor light emitting component correspondsto a point on the straight line connecting point A and point B in thechromaticity diagram of FIG. 6, light of any color in the shaded regionenclosed by points A, B, C and D in FIG. 6 which is the chromaticitypoints (points C and D) of the two or more kinds ofyttrium-aluminum-garnet fluorescent materials of different compositionscan be emitted. According to the second embodiment, color can becontrolled by changing the compositions or quantities of the LEDelements and fluorescent materials. In particular, a light emittingdiode of less variation in the emission wavelength can be made byselecting the fluorescent materials according to the emission wavelengthof the LED element, thereby compensating for the variation of theemission wavelength of the LED element. Also a light emitting diodeincluding RGB components with high luminance can be made by selectingthe emission wavelength of the fluorescent materials.

Moreover, because the yttrium-aluminum-garnet (YAG) fluorescent materialused in the second embodiment has garnet structure, the light emittingdiode of the second embodiment can emit light of high luminance for along period of time. Also the light emitting diodes of the firstembodiment and the second embodiment are provided with light emittingcomponent installed via fluorescent material. Also because the convertedlight has longer wavelength than that of the light emitted by the lightemitting component, energy of the converted light is less than the bandgap of the nitride semiconductor, and is less likely to be absorbed bythe nitride semiconductor layer. Thus, although the light emitted by thefluorescent material is directed also to the LED element because of theisotropy of emission, the light emitted by the fluorescent material isnever absorbed by the LED element, and therefore the emission efficiencyof the light emitting diode will not be decreased.

(Planar light source)

A planar light source which is another embodiment of the presentinvention is shown in FIG. 7.

In the planar light source shown in the FIG. 7, the phosphor used in thefirst embodiment or the second embodiment is contained in a coatingmaterial 701. With this configuration, blue light emitted by the galliumnitride semiconductor is color-converted and is output in planar statevia an optical guide plate 704 and a dispersive sheet 706.

Specifically, a light emitting component 702 of the planar light sourceof FIG. 7 is secured in a metal substrate 703 of inverted C shapewhereon an insulation layer and a conductive pattern (not shown) areformed. After electrically connecting the electrode of the lightemitting component and the conductive pattern, phosphor is mixed withepoxy resin and applied into the inverse C-shaped metal substrate 703whereon the light emitting component 702 is mounted. The light emittingcomponent thus secured is fixed onto an end face of an acrylic opticalguide plate 704 by means of an epoxy resin. A reflector film 707containing a white diffusion agent is arranged on one of principalplanes of the optical guide plate 704 where the dispersive sheet 706 isnot formed, for the purpose of preventing fluorescence.

Similarly, a reflector 705 is provided on the entire surface on the backof the optical guide plate 704 and on one end face where the lightemitting component is not provided, in order to improve the lightemission efficiency. With this configuration, light emitting diodes forplanar light emission which generates enough luminance for the backlight of LCD can be made.

Application of the light emitting diode for planar light emission to aliquid crystal display can be achieved by arranging a polarizer plate onone principal plane of the optical guide plate 704 via liquid crystalinjected between glass substrates (not shown) whereon a translucentconductive pattern is formed.

Now referring to FIG. 8 and FIG. 9, a planar light source according toanother embodiment of the present invention will be described below. Thelight emitting device shown in FIG. 8 is made in such a configurationthat blue light emitted by the light emitting diode 702 is converted towhite light by a color converter 701 which contains phosphor and isoutput in planar state via an optical guide plate 704.

The light emitting device shown in FIG. 9 is made in such aconfiguration that blue light emitted by the light emitting component702 is turned to planar state by the optical guide plate 704, thenconverted to white light by a dispersive sheet 706 which containsphosphor formed on one of the principal plane of the optical guide plate704, thereby to output white light in planar state. The phosphor may beeither contained in the dispersive sheet 706 or formed in a sheet byspreading it together with a binder resin over the dispersive sheet 706.Further, the binder including the phosphor may be formed in dots, notsheet, directly on the optical guide plate 704.

<Application>

(Display device)

Now a display device according to the present invention will bedescribed below. FIG. 10 is a block diagram showing the configuration ofthe display device according to the present invention. As shown in FIG.10, the display device comprises an LED display device 601 and a drivecircuit 610 having a driver 602, video data storage means 603 and tonecontrol means 604. The LED display device 601, having white lightemitting diodes 501 shown in FIG. 1 or FIG. 2 arranged in matrixconfiguration in a casing 504 as shown in FIG. 11, is used asmonochromatic LED display device. The casing 504 is provided with alight blocking material 505 being formed integrally therewith.

The drive circuit 610 has the video data storage means (RAM) 603 fortemporarily storing display data which is input, the tone control means604 which computes and outputs tone signals for controlling theindividual light emitting diodes of the LED display device 601 to lightwith the specified brightness according to the data read from RAM 603,and the driver 602 which is switched by signals supplied from the tonecontrol means 604 to drive the light emitting diode to light. The tonecontrol circuit 604 retrieves data from the RAM 603 and computes theduration of lighting the light emitting diodes of the LED display device601, then outputs pulse signals for turning on and off the lightemitting diodes to the LED display device 601. In the display deviceconstituted as described above, the LED display device 601 is capable ofdisplaying images according to the pulse signals which are input fromthe drive circuit, and has the following advantages.

The LED display device which displays with white light by using lightemitting diodes of three colors, RGB, is required to display whilecontrolling the light emission output of the R, G and B light emittingdiodes and accordingly must control the light emitting diodes by takingthe emission intensity, temperature characteristics and other factors ofthe light emitting diodes into account, resulting in complicateconfiguration of the drive circuit which drives the LED display device.In the display device of the present invention, however, because the LEDdisplay device 601 is constituted by using light emitting diodes 501 ofthe present invention which can emit white light without using lightemitting diodes of three kinds, RGB, it is not necessary for the drivecircuit to individually control the R, G and B light emitting diodes,making it possible to simplify the configuration of the drive circuitand make the display device at a low cost.

With an LED display device which displays in white light by using lightemitting diodes of three kinds, RGB, the three light emitting diodesmust be illuminated at the same time

and the light from the light emitting diodes must be mixed in order todisplay white light by combining the three RGB light emitting diodes foreach pixel, resulting in a large display area for each pixel and makingit impossible to display with high definition. The LED display device ofthe display device according to the present invention, in contrast, candisplay with white light can be done with a single light emitting diode,and is therefore capable of display with white light of higherdefinition. Further, with the LED display device which displays bymixing the colors of three light emitting diodes, there is such a caseas the display color changes due to blocking of some of the RGB lightemitting diodes depending on the viewing angle, the LED display deviceof the present invention has no such problem.

As described above, the display device provided with the LED displaydevice employing the light emitting diode of the present invention whichis capable of emitting white light is capable of displaying stable whitelight with higher definition and has an advantage of less colorunevenness. The LED display device of the present invention which iscapable of displaying with white light also imposes less stimulation tothe eye compared to the conventional LED display device which employsonly red and green colors, and is therefore suited for use over a longperiod of time.

(Embodiment of another display device employing the light emitting diodeof the present invention)

The light emitting diode of the present invention can be used toconstitute an LED display device wherein one pixel is constituted ofthree RGB light emitting diodes and one light emitting diode of thepresent invention, as shown in FIG. 12. By connecting the LED displaydevice and a specified drive circuit, a display device capable ofdisplaying various images can be constituted. The drive circuit of thisdisplay device has, similarly to a case of monochrome display device,video data storage means (RAM)for temporarily storing the input displaydata, a tone control circuit which processes the data stored in the RAMto compute tone signals for lighting the light emitting diodes withspecified brightness and a driver which is switched by the output signalof the tone control circuit to cause the light emitting diodes toilluminate. The drive circuit is required exclusively for each of theRGB light emitting diodes and the white light emitting diode. The tonecontrol circuit computes the duration of lighting the light emittingdiodes from the data stored in the RAM, and outputs pulse signals forturning on and off the light emitting diodes. When displaying with whitelight, width of the pulse signals for lighting the RGB light emittingdiodes is made shorter, or peak value of the pulse signal is made loweror no pulse signal is output at all. On the other hand, a pulse signalis given to the white light emitting diode in compensation thereof. Thiscauses the LED display device to display with white light.

As described above, brightness of display can be improved by adding thewhite light emitting diode to the RGB light emitting diodes. When RGBlight emitting diodes are combined to display white light, one or two ofthe RGB colors may be enhanced resulting in a failure to display purewhite depending on the viewing angle, such a problem is solved by addingthe white light emitting diode as in this display device.

For the drive circuit of such a display device as described above, it ispreferable that a CPU be provided separately as a tone control circuitwhich computes the pulse signal for lighting the white light emittingdiode with specified brightness. The pulse signal which is output fromthe tone control circuit is given to the white light emitting diodedriver thereby to switch the driver. The white light emitting diodeilluminates when the driver is turned on, and goes out when the driveris turned off.

(Traffic signal)

When the light emitting diode of the present invention is used as atraffic signal which is a kind of display device, such advantages can beobtained as stable illumination over a long period of time and no colorunevenness even when part of the light emitting diodes go out. Thetraffic signal employing the light emitting diode of the presentinvention has such a configuration as white light emitting diodes arearranged on a substrate whereon a conductive pattern is formed. Acircuit of light emitting diodes wherein such light emitting diodes areconnected in series or parallel is handled as a set of light emittingdiodes. Two or more sets of the light emitting diodes are used, eachhaving the light emitting diodes arranged in spiral configuration. Whenall light emitting diodes are arranged, they are arranged over theentire area in circular configuration. After connecting power lines bysoldering for the connection of the light emitting diodes and thesubstrate with external power supply, it is secured in a chassis ofrailway signal. The LED display device is placed in an aluminum diecastchassis equipped with a light blocking member and is sealed on thesurface with silicon rubber filler. The chassis is provided with a whitecolor lens on the display plane thereof. Electric wiring of the LEDdisplay device is passed through a rubber packing on the back of thechassis, for sealing off the inside of the chassis from the outside,with the inside of the chassis closed. Thus a signal of white light ismade. A signal of higher reliability can be made by dividing the lightemitting diodes of the present invention into a plurality of groups andarranging them in a spiral configuration swirling from a center towardoutside, while connecting them in parallel. The configuration ofswirling from the center toward outside may be either continuous orintermittent. Therefore, desired number of the light emitting diodes anddesired number of the sets of light emitting diodes can be selecteddepending on the display area of the LED display device. This signal is,even when one of the sets of light emitting diodes or part of the lightemitting diodes fail to illuminate due to some trouble, capable ofilluminate evenly in a circular configuration without color shift bymeans of the remaining set of light emitting diodes or remaining lightemitting diodes. Because the light emitting diodes are arranged in aspiral configuration, they can be arranged more densely near the center,and driven without any different impression from signals employingincandescent lamps.

EXAMPLES

The following Examples further illustrate the present invention indetail but are not to be construed to limit the scope thereof.

Example 1

Example 1 provides a light emitting component having an emission peak at450 nm and a half width of 30 nm employing a GaInN semiconductor. Thelight emitting component of the present invention is made by flowing TMG(trimethyl gallium) gas, TMI (trimethyl indium) gas, nitrogen gas anddopant gas together with a carrier gas on a cleaned sapphire substrateand forming a gallium nitride compound semiconductor layer in MOCVDprocess. A gallium nitride semiconductor having N type conductivity anda gallium nitride semiconductor having P type conductivity are formed byswitching SiH₄ and Cp₂ Mg as dopant gas. The LED element of Example 1has a contact layer which is a gallium nitride semiconductor having Ntype conductivity, a clad layer which is a gallium nitride aluminumsemiconductor having P type conductivity and a contact layer which is agallium nitride semiconductor having P type conductivity, and formedbetween the contact layer having N type conductivity and the clad layerhaving P type conductivity is a non-doped InGaN activation layer ofthickness about 3 nm for making a single quantum well structure. Thesapphire substrate has a gallium nitride semiconductor layer formedthereon under a low temperature to make a buffer layer. The P typesemiconductor is annealed at a temperature of 400° C. or above afterforming the film.

After exposing the surfaces of P type and N type semiconductor layers byetching, n and p electrodes are formed by sputtering. After scribing thesemiconductor wafer which has been made as described above, lightemitting components are made by dividing the wafer with external force.

The light emitting component made in the above process is mounted in acup of a mount lead which is made of silver-plated steel by die bondingwith epoxy resin. Then electrodes of the light emitting component, themount lead and the inner lead are electrically connected by wire bodingwith gold wires 30 μm in diameter, to make a light emitting diode oflead type.

A phosphor is made by dissolving rare earth elements of Y, Gd and Ce inan acid in stoichiometrical proportions, and coprecipitating thesolution with oxalic acid. Oxide of the coprecipitate obtained by firingthis material is mixed with aluminum oxide, thereby to obtain themixture material. The mixture was then mixed with ammonium fluoride usedas a flux, and fired in a crucible at a temperature of 1400° C. in airfor 3 hours. Then the fired material is ground by a ball mill in water,washed, separated, dried and sieved thereby to obtained the desiredmaterial. Phosphor made as describe above is yttrium-aluminum-garnetfluorescent material represented by general formula (Y₀.8 Gd₀.2)₃ Al₅O₁₂ :Ce where about 20%. of Y is substituted with Gd and substitutionratio of Ce is 0.03.

80 parts by weight of the fluorescent material having a composition of(Y₀.8 Gd₀.2)₃ Al₅ O₁₂ :Ce which has been made in the above process and100 parts by weight of epoxy resin are sufficiently mixed to turn intoslurry. The slurry is poured into the cup provided on the mount leadwhereon the light emitting component is mounted. After pouring, theslurry is cured at 130° C. for one hour. Thus a coating having athickness of 120 μm, which contains the phosphor, is formed on the lightemitting component. In Example 1, the coating is formed to contain thephosphor in gradually increasing concentration toward the light emittingcomponent. Irradiation intensity is about 3.5W/cm². The light emittingcomponent and the phosphor are molded with translucent epoxy resin forthe purpose of protection against extraneous stress, moisture and dust.A lead frame with the coating layer of phosphor formed thereon is placedin a bullet-shaped die and mixed with translucent epoxy resin and thencured at 150° C. for 5 hours.

Under visual observation of the light emitting diode formed as describedabove in the direction normal to the light emitting plane, it was foundthat the central portion was rendered yellowish color due to the bodycolor of the phosphor.

Measurements of chromaticity point, color temperature and colorrendering index of the light emitting diode made as described above andcapable of emitting white light gave values of (0.302, 0.280) forchromaticity point (x, y), color temperature of 8080 K and 87.5 forcolor rendering index (Ra) which are approximate to the characteristicsof a 3-waveform fluorescent lamp. Light emitting efficiency was 9.51m/W, comparable to that of an incandescent lamp. Further in life testsunder conditions of energization with a current of 60 mA at 25° C., 20mA at 25° C. and 20 mA at 60° C. with 90% RH, no change due to thefluorescent material was observed, proving that the light emitting diodehad no difference in service life from the conventional blue lightemitting diode.

Comparative Example 1

Formation of a light emitting diode and life tests thereof wereconducted in the same manner as in Example 1 except for changing thephosphor from (Y₀.8 Gd₀.2)₃ Al₅ O₁₂ :Ce to (ZnCd)S:Cu, Al. The lightemitting diode which had been formed showed, immediately afterenergization, emission of white light but with low luminance. In a lifetest, the output diminished to zero in about 100 hours. Analysis of thecause of deterioration showed that the fluorescent material wasblackened.

This trouble is supposed to have been caused as the light emitted by thelight emitting component and moisture which had caught on thefluorescent material or entered from the outside brought aboutphotolysis to make colloidal zinc to precipitate on the surface of thefluorescent material, resulting in blackened surface. Results of lifetests under conditions of energization with a current of 20 mA at 25° C.and 20 mA at 60° C. with 90% RH are shown in FIG. 13 together with theresults of Example 1. Luminance is given in terms of relative value withrespect to the initial value as the reference. A solid line indicatesExample 1 and a wavy line indicates Comparative Example 1 in FIG. 13.

Example 2

In Example 2, a light emitting component was made in the same manner asin Example 1 except for increasing the content of In in the nitridecompound semiconductor of the light emitting component to have theemission peak at 460 nm and increasing the content of Gd in phosphorthan that of Example 1 to have a composition of (Y₀.6 Gd₀.4)₃ Al₅ O₁₂:Ce.

Measurements of chromaticity point, color temperature and colorrendering index of the light emitting diode, which were made asdescribed above and capable of emitting white light, gave values of(0.375, 0.370) for chromaticity point (x, y), color temperature of 4400K and 86.0 for color rendering index (Ra). FIG. 18A, FIG. 18B and FIG.18C show the emission spectra of the phosphor, the light emittingcomponent and the light emitting diode of Example 2, respectively.

100 pieces of the light emitting diodes of Example 2 were made andaverage luminous intensities thereof were taken after lighting for 1000hours. In terms of percentage of the luminous intensity value before thelife test, the average luminous intensity after the life test was 98.8%proving no difference in the characteristic.

Example 3

100 light emitting diodes were made in the same manner as in Example 1except for adding Sm in addition to rare earth elements Y, Gd and Ce inthe phosphor to make a fluorescent material with composition of (Y₀.39Gd₀.57 Ce₀.03 Sm₀.01)₃ Al₅ O₁₂. When the light emitting diodes were madeilluminate at a high temperature of 130° C., average temperaturecharacteristic about 8% better than that of Example 1 was obtained.

Example 4

LED display device of Example 4 is made of the light emitting diodes ofExample 1 being arranged in a 16×16 is matrix on a ceramics substratewhereon a copper pattern is formed as shown in FIG. 11. In the LEDdisplay device of Example 4, the substrate whereon the light emittingdiodes are arranged is placed in a chassis 504 which is made of phenolresin and is provided with a light blocking member 505 being formedintegrally therewith. The chassis, the light emitting diodes, thesubstrate and part of the light blocking member, except for the tips ofthe light emitting diodes, are covered with silicon rubber 506 coloredin black with a pigment. The substrate and the light emitting diodes aresoldered by means of an automatic soldering machine.

The LED display device made in the configuration described above, a RAMwhich temporarily stores the input display data, a tone control circuitwhich processes the data stored in the RAM to compute tone signals forlighting the light emitting diodes with specified brightness and drivemeans which is switched by the output signal of the tone control circuitto cause the light emitting diodes to illuminate are electricallyconnected to make an LED display device. By driving the LED displaydevices, it was verified that the apparatus can be used as black andwhite LED display device.

Example 5

The light emitting diode of Example 5 was made in the same manner as inExample 1 except for using phosphor represented by general formula (Y₀.2Gd₀.8)₃ Al₅ O₁₂ :Ce. 100 pieces of the light emitting diodes of Example5 were made and measured for various characteristics.

Measurement of chromaticity point gave values of (0.450, 0.420) inaverage for chromaticity point (x, y), and light of incandescent lampcolor was emitted. FIG. 19A, FIG. 19B and FIG. 19C show the emissionspectra of the phosphor, the light emitting component and the lightemitting diode of Example 5, respectively. Although the light emittingdiodes of Example 5 showed luminance about 40% lower than that of thelight emitting diodes of Example 5, showed good weatherabilitycomparable to that of Example 1 in life test.

Example 6

The light emitting diode of Example 6 was made in the same manner as inExample 1 except for using phosphor represented by general formula Y₃Al₅ O₁₂ :Ce. 100 pieces of the light emitting diodes of Example 6 weremade and measured for various characteristics.

Measurement of chromaticity point slightly yellow-greenish white lightcompared to Example 1 was emitted. The light emitting diode of Example 6showed good weatherability similar to that of Example 1 in life test.FIG. 20A, FIG. 20B and FIG. 20C show the emission spectra of thephosphor, the light emitting component and the light emitting diode ofExample 6, respectively.

Example 7

The light emitting diode of Example 7 was made in the same manner as inExample 1 except for using phosphor represented by general formula Y₃(Al₀.5 Ga₀.5)₅ O₁₂ :Ce. 100 pieces of the light emitting diodes ofExample 7 were made and measured for various characteristics.

Although the light emitting diodes of Example 7 showed a low luminance,emitted greenish white light and showed good weatherability similar tothat of Example 1 in life test. FIG. 21A, FIG. 21B and FIG. 21C show theemission spectra of the phosphor, the light emitting component and thelight emitting diode of Example 7, respectively.

Example 8

The light emitting diode of Example 8 was made in the same manner as inExample 1 except for using phosphor represented by general formula Gd₃(Al₀.5 Ga₀.5)₅ O₁₂ :Ce which does not contain Y. 100 pieces of the lightemitting diodes of Example 8 were made and measured for variouscharacteristics.

Although the light emitting diodes of Example 8 showed a low luminance,showed good weatherability similar to that of Example 1 in life test.

Example 9

Light emitting diode of Example 9 is planar light emitting device havingthe configuration shown in FIG. 7.

In₀.05 Ga₀.95 N semiconductor having emission peak at 450 nm is used asa light emitting component. Light emitting components are made byflowing TMG (trimethyl gallium) gas, TMI (trimethyl indium) gas,nitrogen gas and dopant gas together with a carrier gas on a cleanedsapphire substrate and forming a gallium nitride compound semiconductorlayer in MOCVD process. A gallium nitride semiconductor layer having Ntype conductivity and a gallium nitride semiconductor layer having Ptype conductivity are formed by switching SiH₄ and Cp₂ Mg as dopant gas,thereby forming a PN junction. For the semiconductor light emittingcomponent, a contact layer which is gallium nitride semiconductor havingN type conductivity, a clad layer which is gallium nitride aluminumsemiconductor having N type conductivity, a clad layer which is galliumnitride aluminum semiconductor having P type conductivity and a contactlayer which is gallium nitride semiconductor having P type conductivityare formed. An activation layer of Zn-doped InGaN which makes adouble-hetero junction is formed between the clad layer having N typeconductivity and the clad layer having P type conductivity. A bufferlayer is provided on the sapphire substrate by forming gallium nitridesemiconductor layer at a low temperature. The P type nitridesemiconductor layer is annealed at a temperature of 400° C. or aboveafter forming the film.

After forming the semiconductor layers and exposing the surfaces of Ptype and N type semiconductor layers by etching, electrodes are formedby sputtering. After scribing the semiconductor wafer which has beenmade as described above, light emitting components are made as lightemitting components by dividing the wafer with external force.

The light emitting component is mounted on a mount lead which has a cupat the tip of a silver-plated copper lead frame, by die bonding withepoxy resin. Electrodes of the light emitting component, the mount leadand the inner lead are electrically connected by wire boding with goldwires having a diameter of 30 μm.

The lead frame with the light emitting component attached thereon isplaced in a bullet-shaped die and sealed with translucent epoxy resinfor molding, which is then cured at 150° C. for 5 hours, thereby to forma blue light emitting diode. The blue light emitting diode is connectedto one end face of an acrylic optical guide plate which is polished onall end faces. On one surface and side face of the acrylic plate, screenprinting is applied by using barium titanate dispersed in an acrylicbinder as white color reflector, which is then cured.

Phosphor of green and red colors are made by dissolving rare earthelements of Y, Gd, Ce and La in acid in stoichiometrical proportions,and coprecipitating the solution with oxalic acid. Oxide of thecoprecipitate obtained by firing this material is mixed with aluminumoxide and gallium oxide, thereby to obtain respective mixture materials.The mixture is then mixed with ammonium fluoride used as a flux, andfired in a crucible at a temperature of 1400° C. in air for 3 hours.Then the fired material is ground by a ball mill in water, washed,separated, dried and sieved thereby to obtained the desired material.

120 parts by weight of the first fluorescent material having acomposition of Y₃ (Al₀.6 Ga₀.4)₅ O₁₂ :Ce and capable of emitting greenlight prepared as described above and 100 parts by weight of the secondfluorescent material having a composition of (Y₀.4 Gd₀.6)₃ Al₅ O₁₂ :Ceand capable of emitting red light prepared in a process similar to thatfor the first fluorescent material, are sufficiently mixed with 100parts by weight of epoxy resin, to form a slurry. The slurry is applieduniformly onto an acrylic layer having a thickness of 0.5 mm by means ofa multi-coater, and dried to form a fluorescent material layer to beused as a color converting material having a thickness of about 30 μm.The fluorescent material layer is cut into the same size as that of theprincipal light emitting plane of the optical guide plate, and arrangedon the optical guide plate thereby to form the planar light emittingdevice. Measurements of chromaticity point and color rendering index ofthe light emitting device gave values of (0.29, 0.34) for chromaticitypoint (x, y) and 92.0 for color rendering index (Ra) which areapproximate to the properties of 3-waveform fluorescent lamp. Lightemitting efficiency of 121 m/W comparable to that of an incandescentlamp was obtained. Further in weatherability tests under conditions ofenergization with a current of 60 mA at room temperature, 20 mA at roomtemperature and 20 mA at 60° C. with 90% RH, no change due to thefluorescent material was observed.

Comparative Example 2

Forming of light emitting diode and weatherability tests thereof wereconducted in the same manner as in Example 9 except for mixing the samequantities of a green organic fluorescent pigment (FA-001 of SynleuchChemisch) and a red organic fluorescent pigment (FA-005 of SynleuchChemisch) which are perylene-derivatives, instead of the firstfluorescent material represented by general formula Y₃ (Al₀.6 Ga₀.4)₅O₁₂ :Ce capable of emitting green light and the second fluorescentmaterial represented by general formula (Y₀.4 Gd₀.6)₃ Al₅ O₁₂ :Cecapable of emitting red light of Example 9. Chromaticity coordinates ofthe light emitting diode of Comparative Example 1 thus formed were (x,y)=(0.34, 0.35). Weatherability test was conducted by irradiating withultraviolet ray generated by carbon arc for 200 hours, representingequivalent irradiation of sun light over a period of one year, whilemeasuring the luminance retaining ratio and color tone at various timesduring the test period. In a reliability test, the light emittingcomponent was energized to emit light at a constant temperature of 70°C. while measuring the luminance and color tone at different times. Theresults are shown in FIG. 14 and FIG. 15, together with Example 9. Aswill be clear from FIG. 14 and FIG. 15, the light emitting component ofExample 9 experiences less deterioration than Comparative Example 2.

Example 10

The light emitting diode of Example 10 is a lead type light emittingdiode.

In the light emitting diode of Example 10, the light emitting componenthaving a light emitting layer of In₀.05 Ga₀.95 N with emission peak at450 nm which is made in the same manner as in Example 9 is used. Thelight emitting component is mounted in the cup provided at the tip of asilver-plated copper mount lead, by die bonding with epoxy resin.Electrodes of the light emitting component, the mount lead and the innerlead were electrically connected by wire boding with gold wires.

Phosphor is made by mixing a first fluorescent material represented bygeneral formula Y₃ (Al₀.5 Ga₀.5)₅ O₁₂ :Ce capable of emitting greenlight and a second fluorescent material represented by general formula(Y₀.2 Gd₀.8)₃ Al₅ O₁₂ :Ce capable of emitting red light prepared asfollows. Namely, rare earth elements of Y, Gd and Ce are solved in acidin stoichiometrical proportions, and coprecipitating the solution withoxalic acid. Oxide of the coprecipitation obtained by firing it is mixedwith aluminum oxide and gallium oxide, thereby to obtain respectivemixture materials. The mixture is mixed with ammonium fluoride used as aflux, and fired in a crucible at a temperature of 1400° C. in air for 3hours. Then the fired material is ground by a ball mill in water,washed, separated, dried and sieved thereby to obtained the first andsecond fluorescent materials of the specified particle distribution.

40 parts by weight of the first fluorescent material, 40 parts by weightof the second fluorescent material and 100 parts by weight of epoxyresin are sufficiently mixed to form a slurry. The slurry is poured intothe cup which is provided on the mount lead wherein the light emittingcomponent is placed. Then the resin including the phosphor is cured at130° C. for 1 hour. Thus a coating layer including the phosphor inthickness of 120 μm is formed on the light emitting component.Concentration of the phosphor in the coating layer is increasedgradually toward the light emitting component. Further, the lightemitting component and the phosphor are sealed by molding withtranslucent epoxy resin for the purpose of protection against extraneousstress, moisture and dust. A lead frame with the coating layer ofphosphor formed thereon is placed in a bullet-shaped die and mixed withtranslucent epoxy resin and then cured at 150° C. for 5 hours. Undervisual observation of the light emitting diode formed as described abovein the direction normal to the light emitting plane, it was found thatthe central portion was rendered yellowish color due to the body colorof the phosphor.

Measurements of chromaticity point, color temperature and colorrendering index of the light emitting diode of Example 10 which was madeas described above gave values of (0.32, 0.34) for chromaticity point(x, y), 89.0 for color rendering index (Ra) and light emittingefficiency of 101 m/W. Further in weatherability tests under conditionsof energization with a current of 60 mA at room temperature, 20 mA atroom temperature and 20 mA at 60° C. with 90% RH, no change due to thephosphor was observed, showing no difference from an ordinary blue lightemitting diode in the service life characteristic.

Example 11

In₀.4 Ga₀.6 N semiconductor having an emission peak at 470 nm is used asan LED element. Light emitting components are made by flowing TMG(trimethyl gallium) gas, TMI (trimethyl indium) gas, nitrogen gas anddopant gas together with a carrier gas on a cleaned sapphire substratethereby to form a gallium nitride compound semiconductor layer in theMOCVD process. A gallium nitride semiconductor layer having N typeconductivity and a gallium nitride semiconductor layer having P typeconductivity were formed by switching SiH₄ and Cp₂ Mg used as the dopantgas, thereby forming a PN junction. For the LED element, a contact layerwhich is gallium nitride semiconductor having N type conductivity, aclad layer which is gallium nitride aluminum semiconductor having P typeconductivity and a contact layer which is gallium nitride semiconductorhaving P type conductivity are formed. An activation layer of non-dopedInGaN with thickness of about 3 nm is formed between the contact layerhaving N type conductivity and the clad layer having P typeconductivity, thereby to make single quantum well structure. A bufferlayer is provided on the sapphire substrate by forming a gallium nitridesemiconductor layer at a low temperature.

After forming the layers and exposing the surfaces of P type and N typesemiconductor layers by etching, electrodes are formed by sputtering.After scribing the semiconductor wafer which is made as described above,light emitting components are made by dividing the wafer with anexternal force.

The light emitting component is mounted in a cup at the tip of asilver-plated copper mount lead by die bonding with epoxy resin.Electrodes of the light emitting component, the mount lead and the innerlead are electrically connected by wire boding with gold wires having adiameter of 30 μm.

The lead frame with the light emitting component attached thereon isplaced in a bullet-shaped die and sealed with translucent epoxy resinfor molding, which is then cured at 150° C. for 5 hours, thereby to forma blue light emitting diode. The blue light emitting diode is connectedto one end face of an acrylic optical guide plate which is polished onall end faces. On one surface and side face of the acrylic plate, screenprinting is applied by using barium titanate dispersed in an acrylicbinder as white color reflector, which is then cured.

Phosphor is made by mixing a fluorescent material represented by generalformula (Y₀.8 Gd₀.2)₃ Al₅ O₁₂ :Ce capable of emitting yellow light ofrelatively short wavelength and a fluorescent material represented bygeneral formula (Y₀.4 Gd₀.6)₃ Al₅ O₁₂ :Ce capable of emitting yellowlight of relatively long wavelength prepared as follows. Namely, rareearth elements of Y, Gd and Ce are solved in acid in stoichiometricalproportions, and coprecipitating the solution with oxalic acid. Oxide ofthe coprecipitation obtained by firing it is mixed with aluminum oxide,thereby to obtain respective mixture material. The mixture is mixed withammonium fluoride used as a flux, and fired in a crucible at atemperature of 1400° C. in air for 3 hours. Then the fired material isground by a ball mill in water, washed, separated, dried and sieved.

100 parts by weight of yellow fluorescent material of relatively shortwavelength and 100 parts by weight of yellow fluorescent material ofrelatively long wavelength which are made as described above aresufficiently mixed with 1000 parts by weight of acrylic resin andextruded, thereby to form a fluorescent material film to be used ascolor converting material of about 180 μm in thickness. The fluorescentmaterial film is cut into the same size as the principal emission planeof the optical guide plate and arranged on the optical guide plate,thereby to make a light emitting device. Measurements of chromaticitypoint and color rendering index of the light emitting device of Example3 which is made as described above gave values of (0.33, 0.34) forchromaticity point (x, y), 88.0 for color rendering index (Ra) and lightemitting efficiency of 101 m/W. FIG. 22A, FIG. 22B and FIG. 22C showemission spectra of the fluorescent material represented by (Y₀.8Gd₀.2)₃ Al₅ O₁₂ :Ce and a fluorescent material represented by generalformula (Y₀.4 Gd₀.6)₃ Al₅ O₁₂ :Ce used in Example 11. FIG. 23 showsemission spectrum of the light emitting diode of Example 11. Further inlife tests under conditions of energization with a current of 60 mA atroom temperature, 20 mA at room temperature and 20 mA at 60° C. with 90%RH, no change due to the fluorescent material was observed. Similarly,desired chromaticity can be maintained even when the wavelength of thelight emtting component is changed by changing the content of thefluorescent material.

Example 12

The light emitting diode of Example 12 was made in the same manner as inExample 1 except for using phosphor represented by general formula Y₃In₅ O₁₂ :Ce. 100 pieces of the light emitting diode of Example 12 weremade. Although the light emitting diode of Example 12 showed luminancelower than that of the light emitting diodes of Example 1, showed goodweatherability comparable to that of Example 1 in life test.

As described above, the light emitting diode of the present inventioncan emit light of a desired color and is subject to less deteriorationof emission efficiency and good weatherability even when used with highluminance for a long period of time. Therefore, application of the lightemitting diode is not limited to electronic appliances but can open newapplications including display for automobile, aircraft and buoys forharbors and ports, as well as outdoor use such as sign and illuminationfor expressways.

What is claimed is:
 1. A light emitting device comprising:a lightemitting component capable of emitting blue light, and a coating membercovering said light emitting component and containing a phosphor capableof absorbing a part of blue light emitted by said light emittingcomponent and emitting light of wavelength different from that of theabsorbed light, wherein the color of said phosphor is yellow and saidcoating member is colored opal by containing a dispersant.
 2. A lightemitting device comprising:a light emitting component capable ofemitting blue light, a coating member covering said light emittingcomponent and containing a phosphor capable of absorbing a part of bluelight emitted by said light emitting component and emitting light ofwavelength different form that of the absorbed light, a molded membersurrounding said light emitting component covered by said coatingmember, wherein the color of said phosphor is yellow and said moldingmember is colored opal by containing dispersant.
 3. A light emittingdevice according to claim 2;wherein said molding member contains thesame phosphor that said coating member contains.
 4. A light emittingdevice according to claim 2;wherein said molding member and said coatingmember are made of the same material.
 5. A light emitting deviceaccording to claim 2;wherein said molding member are made of thematerial selected from the group consisting of epoxy resin, urea resinand silicon resin.
 6. A light emitting device according to claim2;wherein said molding member is formed in a configuration of lens.
 7. Alight emitting device according to claims 1 or 2;wherein said lightemitting component has a nitride compound semiconductor and saidphosphor contains a garnet fluorescent material comprising 1) at leastone element selected from the group consisting of Y, Lu, Se, La, Gd andSm, and 2) at least one element selected from the group consisting ofAl, Ga and In.
 8. A light emitting device according to claims 1 or2;wherein said dispersant is made of material selected from the groupconsisting of barium titanate, titanium oxide, aluminum oxide andsilicon dioxide.